Process for making an improved gasoline



April 15, 1947. w J, SWEENEY 2,418,993

PROCESS FOR MAKING AN IMPROVED GASOLINE Original Filed Aug. 2, 1940 3 Sheets-Sheet 1 April 15, 1947. w. J. swEENEY 2,418,993

PROCESS FOR MAKING AN IMPROVED GASOLINE n Original Filed Aug. 2, 1940 3 Sheets-Sheet 2 YCL ONE .SEPARAT02\ d o e i 2 "y /Z 73 78 I 'l ao had 94 .z/.s rens/olv V SE PAR A 7b4! FIG -JB April 15, 1947. w. J. swr-:ENEY 2,418,993

PROCESS FOR MAKING AN IMPROVED GASOIQNE original Filed Aug. 2, 1940 :s sheets-sneer s MEAT/v con. HEAT/Nc co/l` Ill FRA c 7'/ o NA r1/vc To WE- R lllllllllll 250 EAC-rc2 REACTOR HAT//VC CAS OIL Patented l5,

William J. Sweeney, Summit, N. J., assigner to Standard Oil Development Company. a corpo'- ration of Delaware continuation of 'application semi No. 349,434, August 2, 1940. This application December 28, 1944,sem1N.57o,195

2 claims. l(el. 19e-52) The present invention relates to improvements in the art of treating hydrocarbons. More particularly, the present invention relates to a method of processing a hydrocarbon oil in order to produce a motor fuel or aviation gasoline of improved octane number and good stability.

This application is a continuation of my copending application Serial Number 349,434, led August 2, 1940. Y

It is generally known that cracked gasoline contains appreciable amounts of materials which contribute to instability of the gasoline under severe conditions of'temperature and oxidation.

I have discovered a method of overcoming the aforementioned instability of gasoline under severe conditions of temperature and oxidation which it encounters in operation in van automobile and which is often manifested by octane rating fade Stated briefly at rst, in my process I employ a fresh or regenerated catalyst under certain specified conditions of `temperature and time of treatment wherein I effect polymerization of olens, alkylation of oleflns, isomerization of parafiins and hydrostabilization of unsaturates which are present in a catalytically cracked gasoline and in this manner I improve the quality of the gasoline. More specifically, in a preferred procedure, I first crack a gas oil catalytically, using a once spent catalyst i.- e. a catalyst which has been employed in a prior treatment and then conduct the cracked vapors to a second fractionating zone from which I recover cracked gasoline, normally gaseous hydrocarbons and hydrogen and I conductthese fractions to a zone containing fresh catalyst in which I carry out the aforesaid polymerization of oleflns, hydrogenation of olefins, isomerization of the second fractionation zone only the gasolina.

that is to say, I may separate the gases from the gasoline and treat only the gasoline in the reforming zone.

One object of my invention is to crack, catalytically, a gas oil in the presence of a catalyst which is not unused, newly prepared or regenerated catalyst, but catalyst .which has been employed in a prior conversion, and thereafter reform gasoline produced in the cracking operation, in the presence of fresh or regenerated catalyst.

Another object of my invention is to vaporize a hydrocarbon feed stock, such as a. gas oil, suspend therein a powdered catalyst which has been used in a prior conversion operation, subject 2 the hydrocarbon containing the catalyst suspended therein to cracking temperatures, separate the cracked vapors from the catalyst, and

treat the gasoline fraction in the presence of fresh or regenerated catalyst under ylight naphtha reforming conditions of temperature and pressure.

Other and further objects of my invention will appear from the disclosures contained in the present specification and claims.

Reference is made at this point to the attached drawing in which Figures 1A and 1B show diagrammatically and in partial vertical section a vcombination of apparatus elements in which my invention may Ibe performed continuously using powdered catalyst suspended in the reaction vapors during conversion and Figure 2 is a modiiication thereof employing stationary beds of catalyst to contact reaction vapors.

Referring in detail to Figures 1A and 1B, a charging stock such as an East Texas reduced crude oil having an A. P. I. gravity of about 18 is pumped from line I by pump 2v into a coil 3 disposed in a furnace setting 6 where it is heated to about 825 to 850 F. and thereafter discharged into a transfer line l in communication with ash tower 8 from which tower high boiling hydrocarbons are withdrawn through line 9 while vapors are withdrawn overhead through line I0 and discharged into an injector I2. At the same time, a powdered catalyst such as an acid treated clay, suspended in steam, nitrogen, carbon dioxide, ue gas, etc., which has been contaminated with carbonaceous or tarry deposits as a result of its use in a light naphtha or gasoline reforming operation, as will more fully and at large appear hereinafter, is Withdrawn from conduit I28 and discharged into injector I2 where it admixes with the hydrocarbon vapors. A suspension of hydrocarbon vapors and powdered catalyst is withdrawn from the injector I2 through line 23 and discharged into a cracking coil 28 disposed in a furnace setting 30.

Instead of employing a coil 28, a cylindrical reactor can be employed into which reactor the hydrocarbon gas containing catalyst suspended therein would be injected, and in which reactor the linear velocity of the hydrocarbon gas will .be sufficiently slow, say 2 ft. per second, to permit the catalyst to settle out of the vapors and be withdrawn from the bottom of the reactor.

In the cracking coil or reactor 28 the hydro-` carbon vapors are subjected to cracking condi-y tions of temperature and pressure and remain in the coll for suflicient period of time to effect the desired conversion of the gas oil to gasoline. The cracked products formed in the coil 28 are withdrawn through line 3| and discharged into a cyclone separator 32 where the catalyst is removed from the vapors and passes by gravity through a tower 33, having disposed therein, a plurality of inclined bailes 34, to a receiving hopper 39. 'Ihe vapors, on the other hand, are withdrawn from the cyclone separator through a transfer line 45, thence discharged into a cooling coil 46 where the vapors are cooled below the dew point of the gas oil, thence pass via transfer line 49 into a fractionating column or separator 50 where a liquid fraction consisting essentially of unconverted gas oil may be withdrawn from the bottom of the separator through line 5| and, if desired recycled to line to obtain a, further portion of cracked gasoline therefrom. Normally gaseous components are withdrawn overhead from separator 50 through line 55, while a vapor fraction comprising substantially the gasoline produced is withdrawn from the separator through line 56, thence passed to an injector 51 where it is admixed with fresh or regenerated catalyst. Alternatively both the gasoline vapors and the normally gaseous fractions are withdrawn through conduit 55 and together discharged into injector 51. The fresh' or regenerated catalyst contained in 59 is delivered t'o injector 51 by discharging it from the hopper through star feeder 60 into screw conveyor 62 which latter discharges the catalyst into the chest 63, while steam or the like, discharges through line 65 in the chest 63 forming therein an entrainment of catalyst in steam or the like, which entrainment or suspension is then discharged into the injector 51 forming a new suspension now containing cracked gasoline vapors. The cracked gasoline containing the catalyst suspended is' transferred by means of conduit 68 to a coil 10 disposed in a furnacesetting 1| in which coil the gasoline vapors are subjected to proper conditions of time, temperature and pressure in the coil to effect the desired reforming operation which operation serves to hydrogenate and polymerize the oleflns present as well as to cause isomerization of parans and alkylation of olefins by isoparaiiins. Following the reforming operation, the vapors are withdrawn through transfer line 13 and discharged into cyclone separator 14 where the catalyst is separated from the vapors and passes by gravity through a tower 15 having inclined baflles 16, thence is discharged through star feeder 18 and conduit 19 into a screw conveyor 80. Meanwhile the vapors are withdrawn overhead from the cyclone separator 14 through transfer line 90 and conducted to a cooler.9l and from the cooiervthey are transferred through line 93 to a separator drum 94, where the normally gaseous material is taken ofi. overhead through line 96, while the liquefied reformed gasoline is withdrawn through line .98 as a finished product.

Referring back to the tower 33 in which the catalyst employed in the cracking operation is recovered in the hopper 39, the said catalyst is discharged from the said hopper through a star feeder |00 into a screw conveyor |0I, thence into a dispersion chest |03 where it is suspended in an oxidizing gas such as air, or air diluted with steam, iiue gas, nitrogen, carbonv dioxide, and the like. The oxidizing gas is admitted to the chest or chamber through pipe |04. The dispersion or entrainment of catalyst in regeneration gas is discharged from the chamber |03 ceous deposits contained thereon, and is thence withdrawn from the furnace through line ||0 and discharged into a cyclone separator l I where the catalyst is removed from the regeneration gas and passes by gravity into tower 59 carrying inclined bafiies ||2. The regeneration gas is Withdrawn overhead through line ||4 and the energy content of these gases may be recovered in part by passing them 4through a waste heat boiler or permitting them to expand in a turbine engine. Also, th'e regeneration gas may be used to dilute the air discharged into chamber |03 through line |04. In an operation of this kind, it is necessai-y periodically to replenish the supply of catalyst with fresh or make-up catalyst, and in the present system means are provided for intioducing catalyst into tower 59 through inlet I 0.

Referring now to the catalyst recovered from the reforming operation in tower 15, the same as indicated, is discharged into screw conveyor 80. From the screw conveyor it is passed into a dispersion ch'est |25 where it is suspended or entrained in steam or other gas admitted to the chamber through line |26, and from there the dispersion is conducted through conduit |28 to injector |2 for use without regeneration in the cracking phase as indicated.

In order to give a concrete example illustrating my process, the following operating conditions are set forth with the understanding that my invention is not limited to the precise details set forth therein. Operating on a charging stock comprising a gas oil having an A. P. I. gravity of about 25 good results are obtained in the cracking phase by using a catalyst having a particle size of about 200 to 400 mesh and employing a catalyst to oil ratioof 5 parts of catai lyst to 1 part of oil by weight. In cracking coil 3, a temperatureY of '750 F. to 950 F., depending on the activity of the catalyst used, and a pressure of about 10 lbs. per square inch gauge give satisfactory results. I have found that in the reforming operation satisfactory results are obtained by employing 3 to 4 parts by weight of catalyst to l1 part of oil, employing a temperature somewhat lower than that in the cracking zone, say 650 F. to 850 F., and operating under a. pressure of about 20 lbs. per square inch gauge. The regeneration of the catalyst is carried out in coil |06 preferably under a back pressure of about 2 atmospheres gauge, and the oxygen content of the regeneration gas is preferably about 2% to 20%. In any event, the conditions of pressure and oxygen concentration are controlled to prevent the catalyst from attaining a temperature in substantial excess of 1150 F.

Under the conditions specified, about 40% of the gas oil charged to the system is converted to gasoline and this gasoline has a relatively high octane number and a minimum amount of gumforming constituents. For instance, I may produce a gasoline from an East Texas gas oil under the conditions specied having an octane number of about to 95 according to the rating determined by the Committee on Fuel Research method. f course, the recycled oil will not produce as much gasoline from a given amount thereof as an original virgin gas oil, as the number of its passages through the cracking coil increases, and therefore the liquid product withdrawn through line into separator 50 may periodically be withdrawn from the system and conveyed to a receptacle as a source of fuel oil.

It may be said that the following range of conditions give good results:

Catalyst to oil weight ratio lyst to oil .Regeneration- Temperature 800 F`.1100 F. Pressure p 1-3. atmospheres gauge Time resident in regeneration coil I 2-200 seconds Concentration of oxygen in v regeneration gas 2%-20% As an alternative procedure, I may conduct my process employing a stationary bed or beds of catalyst. Such a process will now be described in connection with the modification illustrated in Fig. II. As will presently appear, in order to maintain continuity of operation, it is necessary to use three reactors containing catalyst so that one may be undergoing regeneration while the other two are in onstream operation, that is to say, one of the two reactors is employed in the cracking operation while the other is employed in reforming the gasoline produced in the cracking operation. In the drawing, the reactors are designated by reference characters R-l, R-2 and R3. These reactors contain a catalyst C which may be disposed in the -three reactors in the form of one continuous f-bed, but preferably the catalyst is disposed on trays, spaced apart, the trays having foraminous bases to permit the flow of oil vapors therethrough.

An operation will now be described assuming that reactor R-l is employed to crack gas oil, while R--z is employed. to reform the gasoline produced in reactor Rl-l. During this assumed period, the catalyst in R3 is undergoing purging and regeneration. In carrying out this cycle, the gas oil is introduced into the system through 1ine 200, thence discharged into coil 204 disposed in a furnace setting 206, where the oil is heated to reaction temperatures, say a temperature of about 825 F., whereupon'it is withdrawn from the furnace through line 201 and then discharged into the 'bottom of reactor R-l which contains once-spent catalyst, that is to say, catalyst which has been used in an operation of reforming gaso- -line for a period of about say 20 minutes. The

gas oil vapors pass upwardly through the catalyst .5-1 to 10-1 cata-` 6 disposed in the reactor R-I, and the total pr uct is withdrawn from the reactor through line 200, thence is discharged into a fractionating column 2I0 from which the higher boiling constituents and unconverted oil are withdrawn from the bottom of the fractionator through line l2| l. The vapor fraction is withdrawn from the fractionator through line 2 I4 and then, if necessary, passed through a second heating coil 2 l 8 disposed in a furnace 2 I1 where the gasoline is heated to reforming temperatures whereupon the vapors are withdrawn from furnace through lines 2|! and 2I9A thence passed into reactor R-2 containing fresh or regenerated catalyst. The gasoline and normally gaseous materials undergo reaction in reactor R-2 in the presence of a catalyst, the principal reaction being polymerization and hydrogenation of olens, accompanied by some alkylation, isomer-ization and cracking. The gasoline thus treated is withdrawn through line 220 as a product to lbe condensed and stabilized in equipment not shown. Meanwhile, the catalyst in R-3 i-s undergoing purging and regeneration, the regeneration gas being discharged into the bottom of the reactor R-,3 through line 222 and withdrawn through line 224. Prior to the regeneration, vsteam may be forced into the reactor through line 222 and rejected through line as indicated, the regeneration gas containing free g oxygen is forced through the catalyst, the operation being preferably carried out under pressure of say about. 45 to'60 lbs. gauge, since this will permit regeneration of the catalyst at lower temperatures, the regeneration gas usually being admitted to the reactor at a temperature of about .v .600 F. to 800 F. and withdrawn at a temperature of about 1100 F. Following the regeneration, the reactor is again treated with steam or some other inert gas to remove air or oxygen. After the operation of cracking followed by reforming has been conducted for a period of about 20 minutes, in .the manner just now explained, during which time the catalyst in reactor R-3 is undergoing regeneration, the same is discontinued andthe gasoil heated in furnace 206 is then conducted from line 201 intoline 226, thence discharged into line 2I9, thence into reactor R-2 which now becomes the reactor 4in which the cracking of the gas oil takes place. As indicated, the catalyst C in reactor Rf-2 is not regenerated immediately following the discontinuance of the reforming operation previously carried out therein. The gas into line 232, thence into the bottom of reactor Rf-B, where they undergo reforming in the same manner as previously explained in connection with the description `of the reforming operation in reactor R-2. The reformed product is recovered through outlet pipe 234 and may be conducted to condensing and stabilizing equipment to produce finished gasoline.

' After the operation, winch has just now been )224, the purpose of the steam being to reymove volatile hydrocarbon material. Thereafter,

described, has been continued for about 20 min' utes, the process is so manipulated as to remove reactor R2 from the onstream operation for the purpose of regenerating the catalyst therein, the catalyst in R-l having undergone regeneration while the cracking operation was proceeding in R-2 and the reforming operation in Rf-3. In carrying out this cycle, the gas oil heated in furnace 206 is discharged as before into line 201, thence into line 226, thence into line 231, thence into line 232, and thence into the reactor R-3 which contains the once-spent catalyst, that is to say, the catalyst which has just been removed from the reforming operation. The gas oil is subjected to the same cracking conditions as previously, in reactors Rf-i and R--2, Whereupon the cracked products are withdrawn through line 238, thence ,discharged into fractionating column 210 from which the unconverted gas oil is discharged through line 2i i. The gasoline and normally gaseous materials are withdrawn through line 2|4, thence discharged into a conduit 240, thence into a furnace 242 where they are heated to reforming temperatures, thence discharged into line 244, thence discharged into line 201A and finally discharged into reactor R-I containing the freshly regenerated catalyst. The gasoline vapors undergo reforming and are recovered from the reactor Rf--l through line 249, from which they may be sent to condensing and stabilizing equipment not shown. After this last described operation has'continued for a period of about 20 minutes in onstream operation, the entire process set forth above is repeated. During the periods when reactor R-Z is oistream, the catalyst therein is purged by conducting steam or some other gas through line 250 into reactor and withdrawing it through line 25|. After suitable purging, the catalyst is regenerated by forcing the regeneration gas through line 250 into the reactor and withdrawing it through line 25E, whereupon the catalyst is again purged. In like manner, the fouled catalyst inR-I is purged and regenerated and again purged, the purging and regenerating gases being forced into the reactor through line 260 and withdrawn through line 26E. It should be pointed out in connection with the operation in the apparatus illustrated in Fig. 2 that a gasoline fraction, substantially free of excess butane and normally gaseous hydrocarbons, may be delivered to the reforming operation. For instance, the gasoline fraction may be taken off from tower 210 at about the level of dashed line 210. This, however, is not the preferred procedure. In operating in the manner illustrated in Fig. 2, I have found that good results are obtained by carrying out a cycle of operations, in which any given reactor is employed for reforming for a period of 20 minutes, thence employed for a 20-minute period as a cracking reactor, and finally undergoes regeneration and purging fora period of 20 minutes.

It is my intention to include in the appended claims not only the precise'details set forth above. but also all modifications thereof falling within the spirit of the said invention.

The invention claimed is:

l. A continuous method for the production of gasoline of high Aoctane number and low degree of unsaturation which comprises vaporizing a gas oil, addingY a. powdered cracking catalyst to said vapors to form suspension of catalyst in said vapors, passing said suspension through a first cracking zone at a temperature between 800 and 950 F., separating the catalyst from the cracked products and regenerating the same, fractionating the said products to recover a gasoline fraction, adding said regenerated catalyst to said gasoline fraction to produce a suspension of said catalyst in said vapors, passing said suspension through a second cracking zone at a temperature up to 850 F., removing a suspension of catalyst in cracked products from said cracking zone, separating the catalyst from said cracked products and mixing thesame without regeneration with the gas oil fed to said first cracking zone as the sole cracking catalyst used therein.

2. A continuous method for the production of gasoline of high octane number and low degree of unsaturation which comprises vaporizing a gas oil, adding a powdered cracking catalyst to said vapors to form a suspension of catalyst in said vapors, passing said suspension through a first cracking zone at a temperature between 800 and 950 F., separating the catalyst from the cracked products and regenerating the same, fractionating the said products to recover a gasoline fraction, adding a more active catalyst than that employed in the said rst zone but one of the same composition, to said gasoline fraction to produce a suspension of said catalyst in said vapors, passing said suspension through a second cracking zone at a temperature up to 850 F., removing a suspension of catalyst in cracked products from said cracking zone, separating the catalyst from said cracked products and mixing the same qwithout regeneration with the gas oil 'fed to said first cracking zone as the sole cracking catalyst used therein.

WILLIAM J. SWEENEY.

REFERENCES CITED The following references are of record in the nie of this patent:

UNITED STATES PATENTS 

